1. 2.7.8 Environmental issues Potential sources and types of
emissions associated with dyeing processes are summarised
in the followins table.
Tab
le 2.1 1: Overview of the typical emissions generated
in dyeing processes
As the table shows, most of the emissions are emissions to
water. Due to the low vapour pressure of the substances in
the dye bath, emissions to air are generally not significant
and can be regarded more as problems related to the
workplace atmosphere (fugitive emissions from
dosing/dispensing chemicals and dyeing processes in "open"
machines). A few exceptions are the thermosol process,
pigment dyeing and those dyeing processes where carriers
are employed. In pigment dyeing the substrate is not
washed after pigment application and therefore the

2. pollutants are quantitatively released to air during drying.
Emissions from carriers are to air and water. In the first part
of the following discussion the environmental issues related
to the substances employed will be described, while in the
second part the environmental issues related to the process
will be mentioned.
2.7.8.1 Environmental issues related to the
substances employed Water-polluting substances in the
above-mentioned emissions may originate from:
78
• the dyes themselves (e.g. toxicity, metals, colour)
• auxiliaries contained in the dye formulation
• basic chemicals (e.g. alkali, salts, reducing and
oxidising agents) and
• auxiliaries used in dyeing processes
• contaminants present on the fibre when it enters the
process sequence (residues of pesticides on wool are
encountered in loose fibre and yarn dyeing and the
same occurs with spin finishes present on synthetic
fibres).
Dyes
• Spent dye baths (discontinuous dyeing),
• residual dye liquors and
• water from washing operations always contain a
percentage of unfixed dye.
The rates of fixation vary considerably among the different
classes of dyes and may be especially low for reactive dyes
(in the case of cotton) and for sulphur dyes. Moreover, large
variations are found even within a given class o fcolourants.
This is particularly significant in the case of reactive dyes.
Fixing rates above 60 % cannot be achieved, for example, in
the case of copper (sometimes nickel) phthalocyanine
reactive dyes especially turquoise green and some marine
shades. In contrast the so called anchor reactive dyes can
achieve extremely high rates of fixation (see Sections 4.6.10
and 4.6.11).

3. The degree of fixation of an individual dye varies according
to type of fibre, shade and dyeing parameters. Therefore
fixation rate values can be given only as approximations.
However, they are useful to give an idea of the amount of
unfixed dyes that can be found in waste water. Information
from different authors is given in the table below.
Table 2.12 % of non-fixed dye that may be discharged in
the effluent for principle classes of dyes
79
As stated earlier, as a consequence of incomplete fixation a
percentage of the dyestuff used in the process ends up in
the waste water. Dyestuffs are not biodegradable in
oxidative conditions, although some of them may degrade
under other conditions (e.g. azo dyes may cleave under
anoxic and anaerobic conditions).

4. Less water-soluble dyestuffs molecules (typically, disperse,
vat, sulphur, some direct dyestuffs and pigments) can be
largely bio-eliminated from waste water by coagulation/
precipitation or absorption/ adsorption to the activated
sludge.
The quantity of activated sludge in the waste water
treatment plant and the quantity of dyestuff to be eliminated
are key factors in determining the efficiency of removal of a
dyestuff from the effluent.
Another factor to take into consideration is the colour
strength of the colourant. For example, with reactive
dyestuffs a lower amount of colourant is needed to achieve a
given shade compared to other classes of dyes (e.g. direct,
vat and sulphur dyes). As a result a lower amount of
dyestuff will need to be removed from the waste water.
Dyestuffs that are poorly bio-eliminable (unless they are
submitted to destructive treatment techniques) will pass
through a biological waste water treatment plant and will
ultimately end up in the discharged effluent.
The First noticeable effect in the receiving water is the
colour. High doses of colour not only cause aesthetic impact,
but can also interrupt photosynthesis, thus affecting aquatic
life.
Other effects are related to organic content of the colourant
(normally expressed as COD and BOD, but could be better
expressed as organic carbon, using TOC, DOC as
parameters), its aquatic toxicity and the presence in the
molecule of metals or halogens that can give rise to AOX
emissions. These issues are discussed in more detail for
each class of dyestuff in Section 9.
Only some general key issues are considered in this section.
AOX emissions
Vat, disperse and reactive dyes are more likely to contain
halogens in their molecule. The content of organically bound
halogen can be up to 12 % on weight for some vat dyes. Vat

5. dyes, however, usually show a very high degree of fixation.
In addition, they are insoluble in water and the amount that
reaches the effluent can be eliminated with high efficiency in
the waste water treatment plant through absorption on the
activated sludge.
Reactive dyes, on the contrary, may have low fixation
degrees (the lowest level of fixation is observed with
phthlocyanine in batch dyeing) and their removal from waste
water is difficult because of the low biodegradability and/or
low level of absorption of the dye onto activated sludge
during treatment. The halogen in MCT (monochlorotriazines)
reactive groups is converted into harmless chloride during
the dyeing process. In calculating the waste water burden it
is therefore assumed that the MCT reactive groups react
completely by fixation or hydrolysis so that they do not
contribute to AOX emissions. However, many commonly
used polyhalogenated reactive dyes, such as DCT
(dichlorotriazine), DFCP (difluorochloropyrimidine) and TCP
(trichloropyrimidine) contain organically bound halogen even
after fixation and hydrolysis. Bound halogen is also found in
discharges of dye concentrates (pad, kitchen) and non-
exhausted dye baths that may still contain unreacted
dyestuff. For the other classes of colourants the AOX issue is
not relevant because, with few exceptions, halogen content
is usually below O.I %. PARCOM 97/1 recommends strict
limits for AOX. Even stricter limits are set by the EU-
Ecolabel and German legislation. Extensive investigation of
AOX in textile effluents was performed, but AOX as an
indicator remains a matter of discussion. 79
80
Dyestuffs containing organically bound halogens (except
fluorine) are measured as AOX. The only way to limit AOX
from dyeing is by dye selection, by more efficient use of
dyes or by treating the resulting effluent by decolouration.
Effluent decolouration can be achieved using destructive
techniques, such as the free radical oxidation or non-

6. destructive techniques (e.g coagulation, adsorption).
However, it should be noted that AOX from dyes do not have
the same effect as the AOX derived from chlorine reactions
(haloform reaction, in particular) arising from textile
processes such as bleaching, wool shrink-resist treatments,
etc.
Dyestliffs are not biodegradable compounds and the
halogens in their molecule should not give rise the haloform
reaction (main cause of hazardous AOX). In this respect it is
interesting to consider that PARCOM 97/1 does not set a
general discharge limit value For AOX. but rather allows
discrimination between hazardous and non-hazardous AOX
[50,OSPAR, 1997].
Heavy metal emission Metals can be present in dyes for two
reasons. First, metals are used as catalysts during the
manufacture of some dyes and can be present as impurities.
Second, in some dyes the metal is chelated with the dye
molecule, forming an integral structural element.
Dye manufactutrers are now putting more effort into
reducing the amount of metals present as impurities. This
can be done by selection of starting products, removal of
heavy metal and substitution of the solvent where the
reaction takes place.
ETAD has established limits in the content of heavy metal in
dyestuffs. The values have been set to ensure that emission
levels from a 2 % dyeing and a total dilution of the dye of
1:2500, will meet the known waste water requirements [64,
BASF, 1994].
Examples of dyes containing bound metals are copper and
nickel in phthalocyanine groups, copper in blue copper-azo-
complex reactive dyes and chromium in metal-complex dyes
used for wool silk and polyamide. The total amount of
metallised dye used is decreasing, but there remain domains
(certain shades such as greens, certain levels of fastness to
light) where phthalocyanine dyes,, for example, cannot be
easily substituted.

7. The presence of the metal in these metallised dyes can be
regarded as a less relevant problem compared to the
presence of free metal impurities. Provided that high
exhaustion and Fixation levels are achieved and that
measures are taken to minimise losses from handling,
weighing, drum cleaning, etc., only a little unconsumed dye
should end up in the waste water. Moreover, since the metal
is an integral part of the dye molecule, which is itself non-
biodegradable, there is very little potential for it to become
bio-available.
It is also important to take into account that treatment
methods such as Filtration and adsorption on activated
sludge, which remove the dye from the waste water, also
reduce nearly proportionally the amount of bound metal in
the final effluent. Conversely, other methods such as
advance oxidation may free the metal.
Toxicitv Dyestuffs
showing aquatic toxicity and/ or allergenic effects are
highlighted in Section 9. Here it is also important to mention
that about 60 % to 70 % of the dyes used nowadays are azo
dyes [77, ELJRATEX. 2000]. Under reductive conditions,
these dyes may produce amines and some of them are
carcinogenic. A list of carcinogenic amines that can be
formed by cleavage of certain azo dves is shown in the Table
2.13. SO
81

8. Table 2.13: List of carcinogenic amines
The use of azo-dyes that may cleave to one of the 22
potentially carcinogenic aromatic amines listed above is
banned according to the 19th amendment of Directive
76/769/EWG on dangerous However, more than 100 dyes
with the potential to form carcinogenic amines are still
available on the market [77, EURATEX, 2000].
Auxiliaries contained in dye formulations
Depending on the dye class and the application method
employed (e.g. batch or continuous dyeing, printing)
different additives are present in the dye formulations. Since
these substances are not absorbed/ fixed by the fibres, they
are completely discharged in the waste water. Typical
additives are listed in the table below.
82

9. Ta
ble 2.14: Ecological properties of dye formulations
additives
While these additives are not toxic to aquatic life, they are in
general poorly biodegradable and not readily bioeliminable.
This applies in particular to the dispersants present in the
formulations of vat, disperse and sulphur dyes. These dyes
are water-insoluble and need these special auxiliaries in
order to be applied to the textile in the form of aqueous
dispersions. These dispersants consist mainly of naphthalene
sulphonate-formaldehyde condensation products and lignin
sulphonates, but sulphomethylation products derived from
the condensation of phenols with formaldehyde and sodium
sulphite can also be found.
Other not readily eliminable additives are acrylate and CMC-
based thickeners and anti-foam agents.
The difference between liquid and powder formulations
should also be mentioned. Dyes supplied in liquid form
contain only one third of the amount of dispersing agent
normally contained in powder dyes (see Table 2.15). The
reason for this difference stems from the manufacturing

10. process of powder dyes: the very small particles generated
during grinding must be protected during the subsequent
drying process and this is possible only by adding high
proportions of dispersing agents.
Table 2.15: Proportion of additives and dye in powder
and liquid dyes
83
Note that liquid formulations include liquid dispersions and
true solutions (solutions without solubilising aids), whereas
powder dyes can be supplied as dusting, free-flowing, non-
dusting powders or granulates.
Basic chemicals and auxiliaries used in the dyeing
process
Regarding the environmental concerns associated with the
chemicals and auxiliaries used in dyeing processes it is
worth mentioning the following key issues.
Sulphur containing reducing agents
Waste water from sulphur dyeing contains sulphides used in
the process as reducing agents. In some cases the sulphide
is already contained in the dye formulation and in some
other cases it is added to the dye bath before dyeing. In the
end, however, the excess of sulphide ends up in the waste
water. Sulphides are toxic to aquatic organisms and
contribute to increasing COD load. In addition, sulphide
anions are converted into hydrogen sulphide under acidic
conditions, thereby giving rise to problems of odour and
corrosivity. .

11. Sodium hydrosulphite (also called sodium dithionate) is
another sulphur-containing reducing agent, which is
commonly used not only in sulphur and vat dyeing
processes, but also as reductive after-cleaning agent in PES
dyeing. Sodium hydrosulphite is less critical than sodium
sulphide. However, during the dyeing process sodium
dithionite is converted into sulphite (toxic to fish and
bacteria) and in some cases this is further oxidised into
sulphate. In lhe waste water treatment plant sulphite is
normally oxidised into sulphate, but this can still cause
problems. Sulphate, in fact, may cause corrosion of concrete
pipes or may be reduced under anaerobic conditions into
hydrogen sulphide.
Hydroxyacetone, although it produces an increase in COD
load, is recommended to lower the sulphur content in waste
water, but it cannot replace hydrosulphite in all applications.
New organic reducing agents with improved reducing effects
have been developed (see Section 4.6.5 and Section 4.6.6
for further details).
Consumption of the reducing agent by the oxygen present in
the machine (partially-flooded dyeing machines) needs also
to be taken into account. Instead of applying only the
amount of reducing agent required for the reduction of the
dyestuff, a significant extra amount of reducing agent often
needs to be added to compensate for the amount consumed
by the oxygen contained in the machine. This obviously
increases oxygen demand of the effluent.
Oxidising agents Dichromate should no longer be used in
Europe as an oxidising agent when dyeing with vat and
sulphur dyes, but it is still widely used for the fixation of
chrome dyes in wool dyeing. Chromium III exhibits low
acute toxicity, while chromium VI is acutely toxic and has
been shown to be carcinogenic towards animals. During the
dyeing processes with chrome dyes, Cr VI 'is reduced to Cr
III if the process is under control. Nevertheless, emissions of
Cr VI may still occur due to inappropriate handling of

12. dichromate during dye preparation (care must be taken as
dichromate is carcinogenic and may cause health problems
for workers handling it).
Emissions of trivalent chromium in the waste water can be
minimised (see Section 4.6.15), but cannot be avoided,
unless alternative dyestuffs are applied (see Section 4.6.16).
The use of bromate, iodate and chlorite as oxidising agents
in vat and sulphur dyeing processes and the use of
hypochlorite as stripping agent for decolouring faulty goods
or for cleaning dyeing machines (e.g. before subsequent
lighter-coloured dyeing) may produce AOX emissions.
However, only hypochlorite and elemental-chlorine-
containing compounds (e.g. certain chlorite products that
contain Cl2 or use chlorine as activator for formation of
chlorine dioxide gas) are likely to give rise to hazardous AOX
83
84
Salt
Salts of various types are used in dyeing processes for
different purposes (e.g to promote level dyeing or to
promote dye erhaustion).. In particular, large amounts of
salt are used in cotton batch dyeing processes with reactive
dyes. The amount of salt employed is quite significant
compared to other classes of dyestuffs, for example direct
dyes (Table 2.16) and efforts have been made by dye
manufacturers to solve this problem (see Section 4.6.1 1).
Table 2.16: Amount of salt employed in cotton batch
dyeing processes with reactive and direct dyes

13. In addition to the use of salt as raw material, neutralization
of commonly used acids and alkalis produces salts as a by-
products. Salts are not removed in conventional waste water
treatment systems and they are therefore ultimately
discharged in the receiving water.
Although the mammalian and aquatic toxicity of the
commonly employed salts are very low, in arid or semi-arid
regions their large-scale use can produce concentrations
above the toxic limit and increase the salinity of the
groundwater. Countries have set emission limits at 2000
ppm or below. River quality standards must also be taken
into account.
Carriers The use of these auxiliaries, which were widely
employed in the past, has now been reduced due to
ecological and health problems. They are still an issue in
dyeing of polyester in blend with wool.
Carriers may already be added to the dyes by
manufacturers. In this case textile finishers will have little
knowledge of the loads discharged ([4, Tebodin, 1991] and
[61, L. Bettens, 1999]).
Carriers (sec Section 8.6.7) include a wide group of organic
compounds, many of them steam volatile, poorlv
biodegradable and toxic to humans and aquatic life.
However, as the active substances usually have high affinity
for the fibre (hydrophobic types), 75 - 90 % are absorbed by
the textile and only the emulsifiers and the hydrophilic-type
carriers such as phenols and benzoate derivatives are found
in the waste water.
The carriers that remain on the fibre after dyeing and
washing, are partially volatilised during drying and fixing
operations and can give rise to air emissions. Traces can still
he found on the finished product, thus representing a
potential problem for the consumer. Alternative options are
described in Sections 4.6.1 and 4.6.2.
Other auxiliaries of environment interest

14. Other substances that may be encountered in the dyeing
auxiliaries and that may give rise to water pollution are:
85
• fatty amine ethoxylates (levelling agent)
• alkylphenol ethoxylates (levelling agent)
• quaternary ammonium compounds (retarders for
cationic dyes)
• polyvinylpyrrolidone (levelling agent for vat, sulphur
and direct dyes)
• cyanamide-ammonia salt condensation products
(auxiliaries for fastness improvement)
• Acrylic acid-maleic acid copolymers (dispersing agent)
• Ethylene diamine tetra acetate (EDTA)
• diethylenetriaminepentaacetate (DTPA)
• ethylenediaminetetra(methylenephosphonic acid)
(EDTMP)
• diethylenetriaminepenta(methylenphosphonic acid)
(DTPMP)
These are water-soluble hard-to-biodegrade compounds
which can pass untransformed or only partially degraded,
through waste water treatment systems. In addition, some
of them are toxic (e.g. quaternary amines) or can give rise
to metabolites which may affect reproduction in the aquatic
environment (APEO).
2.7.8.2 Environmental issues related to the process
Both water and energy consumption in dyeing processes are
a function of the dyeing technique, operating practices and
the machinery employed.
Batch dyeing processes generally require higher water and
energy consumption levels than continuous processes. This
is due number of different factors
The higher liquor ratios involved in batch dyeing represent
one of these factors. As previously mentioned in Section
2.7.2, higher liquor ratios mean not only higher water and
energy uses, but also a higher consumption of those
chemicals and auxiliaries that are dosed based on the

15. volume of the bath. Consistently with the quality of the
different types of substrates, all equipment manufacturers
now can offer machines with reduced liquor ratios. Terms
like "low liquor ratio''and "ultra-low liquor ratio" are now
commonly used to define the performance/ features of
modern machines, for dyeing fabric in rope form.
Nominal reference values for "low liquor ratio machines" are
in the range of 1:5-1:8 for cotton and correspondingly
1:3-1:4 for PES. The liquor ratio can be higher for other
types of substrates/fibres.
The term "Ultra-low liquor ratio" is used to define machines
that can be operated at liquor ratios as low as the minimum
volume required to completely wet out the substrate and
avoid cavitations of the pumps. This term applies only to
machines for dyeing fabric in rope form.
It is important to show the difference between the nominal
and real liquor ratios. As already stated in Section 2.7.2, the
nominal liquor ratio is the liquor ratio at which a machine
can be operated when it is loaded at its maximum/ optimal
capacity. It is often the case that the machine is
underloaded compared to its optimal capacity. This often
occurs in commission companies where a high production
flexibility is required to serve variable lot sizes according to
customer's demands. Modern machines can still be operated
at approximately constant liquor ratio whilst being loaded at
a level as low as 60 % of their nominal capacity (or even 30
% of their nominal capacity with yarn dyeing machines - see
Section 4.6.19). In this way the same benefits achievable
with low liquor ratios can be kept even with reduced loading.
It is obvious however, that when a machine is loaded far
below its optimal capacity (e.g. below 60 % of its nominal
capacity for fabric dyeing machines) the real liquor ratio will
differ greatly from the nominal liquor ratio. This will result
not only in lower environmental performances (higher water,
energy and chemicals consumptions), but also in higher
operating costs.
86

16. In conclusion, the use of low liquor ratio machinery, or
selection of the most adequate machine for the size of the
lot to be processed, is fundamental to the resultant
environmental performance of the process. Having said that.
high energy and water consumption in batch dyeing is not
only the result of high liquor ratios.
Another factor to take into consideration is the
discontinuous nature of the batch dyeing operating mode,
especially with regard to operations such as cooling,
heating, washing and rinsing.
Furthermore, shade matching can be responsible for higher
water and energy consumption, especially when dyeing is
carried out without the benefit of laboratory instruments. In
a manual regime the bulk of the dyestuff is normally applied
in the first phase to obtain a shade which is close to that
required in the final product. This is followed by a number of
matching operations, during which small quantities of dye
are applied to achieve the final shade. Shades which are
difficult to match may require repeated shade additions with
cooling and reheating between each addition [32, ENco,
2001].
Increased energy and water consumption may also be
caused by inappropriate handling techniques and/or poorly
performing process control systems. For example, in some
cases displacement spillage may occur during immersion of
the fibre in the machine, while the potential for overfilling
and spillage exists where the machines are only equipped
with manual control valves, which fail to control the liquor
level and temperature correctly (see also Section 4.1.4).
Continuous and semi-continuous dyeing processes
consume less water, but this also means a higher dyestuff
concentration in the dye liquor. In discontinuous dyeing the
dye concentration varies from O.I to I g/l, while in
continuous processes this value is in the range of 10 to 100
g/l. The residual padding liquor in the troughs, pumps and
pipes must be discarded when a new colour is started. The
discharge of this concentrated effluent can result in a higher

17. pollution load compared with discontinuous dyeing,
especially when small lots of material are processed.
However, modern continuous dyeing ranges have steadily
improved in recent years. The use of small pipes and pumps
and small pad-bath troughs help to reduce the amount of
concentrated liquor to be discharged.
In addition, it is possible to minimise the discard of
leftovers, by using automated dosing systems, which meter
the dye solution ingredients and deliver the exact amount
needed (see also Sections 4.1.3 and 4.6.7 for more detailed
information about recent improvements).
In hoth continuous and batch dyeing processes, final
washing and rinsing operations are water- intensive steps
that need to be taken into consideration. Washing and
rinsing operations actually consume greater quantities of
water than dyeing itself (see Sections 4.9.1 and 4.9.2 for
water and energy conservation techniques in batch and
continuous processing and Sections 4.1.4 and 4.6.19 for
equipment optimisation in batch processing).
Printing
2.8.3 Environmental issues Emission sources typical of
printing processes are:
• printing paste residues
• waste water from wash-off and cleaning operation'
• volatile organic compounds from drying and fixing
processes
97
Printing paste residues Printing paste residues are
produced for different reasons during the printing process
and the amount can be particularly relevant (Section
3.3.3.5.5 provides information about consumption and
emission levels). Two main causes are, for example,

18. incorrect measurements and the common practice of
preparing excess paste to prevent a shortfall. Moreover, at
each colour change, printing equipment and containers
(dippers, mixers. homogenizers, drums, screens, stirrers,
squeegees, etc.) have to be cleaned up. Print pastes adhere
to every implement due to their high viscosity and it is
common practice to use dry capture systems to remove
them before rinsing with water. In this way these residues
can at least be disposed of in segregated form, thus
minimising water contamination. Another significant, but
often forgotten source of printing paste residues is the
preparation of sample patterns. Sometimes they are
produced on series production machines, which means high
specific amounts of residues produced. There are techniques
available that can help to reduce paste residues (see Section
4.7.4) and techniques for recovery/re-use of the surplus
paste (see Sections 4.7.5 and 4.7.6). Their success is,
however, limited due to a number of inherent technological
deficiencies of analogue printing technology. Most of these
deficiencies are related to the analogue transfer of the
pattern, the unavoidable contact between the surface of the
substrate and the applicator (screen) and the need for
thickeners in the formulation (paste rheology), which limits
the ultimate potential for paste re-use. Digital printing offers
a solution to these problems (see Sections 4.7.8 and 4.7.9).
Waste water from wash-off and cleaning operations
Waste water in printing processes is generated primarily
from final washing of the fabric after fixation, cleaning of
application systems in the printing machines, cleaning of
colour kitchen equipment and cleaning of belts. Waste water
from cleaning-up operations accounts for a large share of
the total pollution load. even mOre than water from wash-
offoperations. Emission loads to water are mainly
attributable to dyestuff printing processes because in the
case of pigment printing, although considerable amounts of
waste water arise from cleaning operations, pigments are
completely fixed on the fibre without need for washing-off.

19. Pollutants that are likely to be encountered in waste water
are listed in the table below.
98
Ta
ble 2.17: Pollutants that are more likely to be encountered
in waste water from printing processes
Volatile organic compounds from drying and fixing
Drying and fixing are another important emission source in
printing processes. The following pollutants may be
encountered in the exhaust air [179, DBA, 2001]:
• aliphatic hydrocarbons (C10-C20) from binders
• Monomers such as acrylates, vinyl acetates, styrene,
acrylonitrile, methylol acrylamide, butadiene,
• • methanol from fixing agents

20. • • other alcohols, esters, polyglycols from emulsifiers
• • formaldehyde from fixation agents
• • ammonia from urea decomposition and from
ammonia present, for example, in pigment printing
pastes)
• • N-methylpyrrolidone from emulsifiers
• • phosphoric acid esters
• • phenycyclohexene from thickeners and binders.
A more comprehensive list of pollutants potentially present
in the exhaust air from heat treatment after printing with an
indication of the potential source, is given in Section 12.
Finishing
2.9.2.8 Anti felt treatment fo wool
Anti-felt finishing is applied in order to provide anti-felt
properties to the good. This will prevent shrinking of the
finished product when it is repetitively washed in a laundry
machine. Two treatments, which are also complementary,
are applied:
• oxidising treatment (subtractive treatment)
• treatment with resins (additive treatment).
These treatments can be applied at any stage of the process
and on all different make-ups. They are most commonly
applied on combed tops for specific end-products (e.g.
underwear
102
Oxidising treatments
In the oxidising treatment the specific chemicals used attack
the scales of the cuticles and chemically change the external
structure of the fibre. This treatment has traditionally been
carried out using one of the following chlorine-releasing
agents:
• sodium hypochlorite
• sodium salt dichloroisocyanurate
• active chlorine (no longer used).

21. The oldest process is the one using sodium hypochlorite.
However, since the development of active chlorine is difficult
to control, wool fibre characteristics can be deeply changed,
also giving irregular results.
Dichloroisocyanurate is more advantageous here because it
has the ability to release chlorine gradually, thereby
reducing the risk of fibre damage. The process with
dichloroisocyanurate (Basolan process licensed by BASF)
consists in impregnating the material in a bath (35°C)
containing the oxidant, sodium sulphate and an auxiliary
(surfactant). After 20 - 30 min the material is rinsed, then it
is submitted to an anti- chlorine treatment with 2-3% of
sodium bisulphite and rinsed again.
All these chlorine-based agents have recently encountered
restrictions because they react with components and
impurities (soluble or converted into soluble substances) in
the wool, to form absorbable organic chlorine compounds
(AOX).
Alternative oxidising treatments have therefore been
developed. In particular, peroxysulphate, permanganate,
enzymes and corona discharge come into consideration.
However, the only alternative to chlorine-based agents
readily available today is peroxysulphate. The process with
peroxysulphate compounds is quite similar to the chlorine
treatment, but does not involve the use of chlorine and does
not generate chloroamines.
The material is treated with the oxidising agent in acid liquor
at room temperature until the active oxygen has been
largely consumed.
Both with chlorine based agents and peroxysulphate, sodium
sulphite is then added as an anti- oxidant to the same liquor
at slightly alkaline pH. This is a reductive after treatment to

22. avoid damage and yellowing of the wool fibre at alkaline
pH. The goods are subsequently rinsed. If necessary, they
are treated with a polymer (see treatments with resins
below).
Treatments with resins (additive processes) In additive
processes, polymers are applied to the surface of the fibre
with the aim of covering the scales with a "film". However,
this treatment must be regarded as a pseudo felt-free
finishing process, as it is not the felting propensity that is
reduced, but merely the effect thereof.
The polymer must have a high substantivity for wool.
Cationic polymers are the most suitable for this treatment
because, after the previous oxidative and reductive
pretreatment, the wool surface becomes anionic. The
polymer may be. in some case, sufficiently effective on its
own to make pretreatment unnecessary. However, the
combination of subtractive and additive processes has the
greatest technical effect,
102
103
Combined treatments (Hercosett Process)
The oldest combination process is the so called Hercosett
process (by C.S.I.R.O), which consists in chlorine
pretreatment followed by application of a polyamide-
epichloridrine resin. Whilst the Hercosett process can be
carried out in batch or continuous mode, the latter is
predominant nowadays.
The continuous process consists of the following steps (see
Figure 2.27):
1. chlorine treatment in acid medium (using chlorine gas
or sodium hypochlorite)
2. reduction of chlorine using sulphite in the same bath
3. rinsing
4. neutralisation with sodium carbonate

23. 5. rinsing
6. resin application
7. softener application
8. drying and polymerisation.
The Hercosett process has been widely used for years as
anti-felt Finishing of wool in different states (loose fibre,
combed top, yarn, knitted and woven fabric) due to its low
cost and high quality effects
However, the effluent shows high concentrations of COD and
AOX.
The formation of AOX is attributable not only to the oxidant,
but also to the resin. In fact, the typical resin applied in the
Hercosett process is a cationic polyamide whose
manufacturing process involves the use of epichloridrine,
which is another source of the chlorinated hydrocarbons in
the effluent.
Alternative resins have been developed, based on
polyethers, cationic aminopolysiloxanes synergic mixtures of
polyurethanes and polydimethylsiloxanes, but they all have
some limitations concerning their applicability. New
processes have also been developed, but so far the results
achieved with the Hercosett process cannot be fully matched
by any alternative, which is why it is still the preferred
process particularly for treatments such as the anti-felt
finishing of combed tops.
Environmental issues in Finishing
2 9 3 Environmental issues
Among textile finishing processes, the chemical ones are
those that are more significant from the point of view of the
emissions generated. As in dyeing, the emissions are quite
different between continuous and discontinuous processes.
Therefore this distinction will be used in the
104

24. discussion of the main environmental issues associated
with finishing. Anti-felt treatments represent a peculiar type
of finishing both in terms of applied techniques and
emissions. The environmental issues related to this process
are therefore discussed in Section 2.9.2.8 together with tile
description of the process itself.
Environmental issues associated with continuous
Finishing processes
With some exceptions (e.g. application of phosphor-organic
flame retardants) finishing processes do not require
washing operations after curing. This means that the
possible emissions of water pollution relevance are restricted
to the system losses and to the water used to clean all the
equipment.
In a conventional foulard, potential system losses at the end
of each batch are:
• the residual liquor in the chassis
• the residual liquor in the pipes
• the leftovers in the batch storage container from which the
finishing formulation is fed to the chassis.
Normally these losses are in the range of 1-5%, based on
the total amount of liquor consumed: it is also in the
finisher's interest not to pour away expensive auxiliaries.
However, in some cases, within small commission finishers,
losses up to 35 or even 50 % may be observed. This
depends on the application system (e.g. size of foulard
chassis) and the size of the lots to he finished
In this respect, with application techniques such as spraying.
foam and slop-padding (to a lower extent due to high
residues in the system) system-losses are much lower in
terms of volume (although more concentrated in terms of
active substance). Residues of concentrated liquors are re-
used, if the finishing auxiliaries applied show sufficient

25. stability, or otherwise disposed of separately as waste
destined to incineration.
However, too often these liquors are drained and mixed with
other effluents. Although the volumes involved are quite
small when compared with the overall waste water volume
produced by a textile mill, the concentration levels are very
high, with active substances contents in the range of 5-25%
and COD of 10 to 200 g/litre.
In the case of commission finishing mills working mainly on
short batches, the system losses can make up a
considerable amount of the overall organic load.
In addition, many substances are difficult to biodegrade or
are not biodegradable at all and sometimes they are also
toxic (e.g. biocides have a very low COD, but are highly
toxic).
The range of pollutants that can be found in the waste water
varies widely depending on the type of finish applied.
The typical pollutants and the environmental concerns
associated with the use of the most common finishing
agents are discussed in Section 8.8. I
In particular, the release of the following, substances in the
environment gives rise to significant concerns:
• ethylene urea and melamine derivatives in their "not
cross-linked form" (cross-linking agents in easy-care
finishes)
• organo-phosphorolis and polybrominated organic
compounds (flame retardant agents)
• polysiloxanes and derivatives (softening agents)
• alkyl phosphates and alkylelherphosphates (antistatic
agents)
• fluorochemical repellents.

26. In the drying and curing operation air emissions are
produced due to the volatility of the active substances
themselves as well as that of their constituents (e.g.
monomers, oligomers, impurities and decomposition by-
products).
Furthermore air emissions (sometimes accompanied by
odours) are associated with the residues of preparations and
fabric carry-over from upstream processes (for example,
polychlorinated dioxins/furans may arise from the thermal
treatment of textiles that have been previously treated with
chlorinated carriers or perchloroethylene).
104
105
The emission loads depend on the drying or curing
temperature, the quantity of volatile substances in the
Finishing liquor, the substrate and the potential reagents in
the formulation.
The range of pollutants is very wide and depends on the
active substances present in the formulation and again on
the curing and drying parameters.
In most cases, however, the emissions produced by the
single components of the finishing recipes are additive. As a
result. the total amount of organic emissions in the exhaust
air (total organic carbon and specific problematic compounds
such as carcinogenic and toxic substances) can easily be
calculated by means of emission factors given for the
finishing recipes by manufacturers (see also Section 4.3.2).
Note however, that Germany is the only Member State
where there is a fully developed system in which the
manufacturers provide the finisher with such information on
the "products supplied. Another important factor to consider
regarding air emissions is that the directly heated (methane,
propane, butane) stenters themselves may produce relevant
emissions (non- combusted organic compounds, CO, NO,,

27. formaldehyde). Emissions, for example, of formaldehyde up
to 300 g/h (2 - 60 mg/m3) have been observed in some
cases, which were attributable to inefficient combustion of
the gas in the stenter frame [179, UBA, 2001].
It is therefore obvious - when speaking about air emissions -
that the environmental benefit obtained with the use of
formaldehyde-free finishing recipes is totally lost if the
burners in the stenter frames are poorly adjusted and
produce high formaldehyde emissions. The active
substances in the most common finishing agents and the
possible associated air emissions are discussed in Section
8.8. Moreover a more comprehensive list of pollutants that
can be found in the exhaust air from heat treatments in
general, is reported in Section 12.
Environmental issues associated with discontinuous
processes The application of functional finishes in long
liquor by means of batch processes is used mainly in varn
finishing and in the wool carpet yam industry in particular.
Since the functional finishes are generally applied either in
the dye baths or in the rinsing baths after dyeing,, this
operation does not entail additional water consumption with
respect to dyeing.
For the resulting water emissions, as with batch dyeing, the
efficiency of the transfer of the active substance from the
liquor to the fibre is the key factor which influences the
emission loads. The efficiency depends on the liquor ratio
znd on many parameters such as pH, temperature and the
type of emulsion (micro- or macro-emulsion).
Maximising the efficiency is particularly important when
biocides are applied in mothproofing finishing. As
mothproofing agents are not water-soluble they are applied
from emulsions. The degree of emulsification and the pH are
critical in the application of mothproofing agents (i.e. the
efficiency of the process is higher when the active substance

28. is applied from micro-emulsions and at acidic pH). Note here
that the finishing agents are dosed based on the weight of
the fibre and not on the amount of bath (in g/litre). The
pollutants that may be encountered in waste water vary
depending on the finishing agents applied: Section 8.8 gives
more details. The main issues worth mentioning are the
application of mothproofing agents (emissions of biocides)
and the low level of exhaustion of softeners (emissions of
poorly biodegradable substances).